CN111334266B - Profile control agent and preparation method and application thereof - Google Patents
Profile control agent and preparation method and application thereof Download PDFInfo
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- CN111334266B CN111334266B CN201811550157.6A CN201811550157A CN111334266B CN 111334266 B CN111334266 B CN 111334266B CN 201811550157 A CN201811550157 A CN 201811550157A CN 111334266 B CN111334266 B CN 111334266B
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Abstract
The invention relates to the technical field of profile control of oil fields, and discloses a profile control agent, and a preparation method and application thereof. The profile control agent comprises: water-soluble thickening agent, modified cross-linking agent, stabilizing agent, pH regulator and water; wherein the modified crosslinking agent is alkylguanidine modified polyethyleneimine. The profile control agent provided by the invention can realize time-delay controllable crosslinking, and the jelly has certain strength and a sterilization effect, so that one agent has multiple purposes.
Description
Technical Field
The invention relates to the technical field of profile control of oil fields, in particular to a profile control agent and a preparation method and application thereof.
Background
Profile control means that a plugging agent system is injected from a water injection well to plug a high permeable formation, so that the absorption profile of a water injection interval is adjusted, the heterogeneity of an oil reservoir is improved, the aim of reservoir balanced displacement is fulfilled, and the method is an effective way for improving the water flooding development effect.
The water shutoff and profile control technology is an important means for improving the heterogeneity of a reservoir under low oil price, realizing balanced displacement and stable yield of an oil field. The existing plugging agent mainly comprises polymer jelly, gel, particles, foam, microorganisms and the like, wherein a jelly system is the plugging agent which is most used and most widely applied in the plugging and plugging technology, and the system takes partially Hydrolyzed Polyacrylamide (HPAM) as a main agent and Cr as a main agent3+、Al3+Phenolic resin, phenol, resorcinol, and the like as a crosslinking agent. The jelly belongs to a profile control system with high crosslinking strength and has relatively high mineralization and temperature in an oil layerUnder the condition of high temperature, the stability of the system is deteriorated due to the degradation of the polymer (thermal degradation, salt degradation, metal ion degradation, etc.). In addition, chromium jelly and the like are also accompanied with environmental problems such as pollution of high-valence metal ions in application. Therefore, the gel system which has the gelling temperature of 50-90 ℃, has stable product performance and meets the environmental protection requirement is developed, and the gel system has important significance for the sustainable development of the water shutoff profile control technology.
Polyethyleneimine (PEI) as an environment-friendly crosslinking agent has wide application potential due to its unique crosslinking mechanism. The existing research shows that the gel system formed by PEI and HPAM has the advantages of good temperature resistance and salt tolerance, large depth of treated stratum, high strength, good stability and the like. This is mainly due to the low viscosity of the HPAM solution and the crosslinker solution, which can easily enter the high permeability zone or crack of the formation during the injection process. Under the condition of a stratum at a certain temperature, the injected HPAM solution and the crosslinking agent solution are subjected to crosslinking reaction after a period of reaction time to form a high-strength gel system, and a certain plugging effect is generated on a stratum high-permeability zone or a crack, so that delay controllable crosslinking is realized. The HPAM/PEI gel system has been widely applied to various large oil fields abroad due to the excellent performance, and more than 350 operations are successfully applied. At present, domestic research is still in an experimental stage, and mainly focuses on formula optimization and crosslinking mechanism research of a PEI (polyetherimide) jelly system. Although the HPAM/PEI gel system has a plurality of advantages, the gel forming time at high temperature is too short, and the requirement of water shutoff and profile control of a high-temperature oil well is difficult to meet. In order to realize industrialization of the HPAM/PEI gel system, the problems of too short gel forming time and uncontrollable gel forming time at high temperature must be solved. Therefore, the development of a polyethyleneimine gel system with a crosslinking delaying performance is a key direction.
In addition, the oilfield injection water is generally oilfield sewage, microorganisms such as Sulfate Reducing Bacteria (SRB), saprophytic bacteria (TGB) and iron bacteria exist in the oilfield injection water, and a series of problems such as polymer biodegradation, stratum blockage and equipment corrosion are easily caused.
Disclosure of Invention
The invention aims to solve the problems that the gelling time of the existing polyethyleneimine profile control agent is too short, the gelling time is uncontrollable and the bacteria content of oilfield sewage is high, and provides a profile control agent, and a preparation method and application thereof. The profile control agent realizes time-delay controllable crosslinking, and the jelly has certain strength and a sterilization effect, thereby realizing multiple purposes of one agent.
In order to achieve the above object, a first aspect of the present invention provides a profile control agent comprising: water-soluble thickening agent, modified cross-linking agent, stabilizing agent, pH regulator and water; wherein the modified crosslinking agent is alkylguanidine modified polyethyleneimine.
In a second aspect, the present invention provides a process for preparing the profile control agent, which comprises:
(1) adding polyacrylamide into water under stirring state until the polyacrylamide is uniformly dissolved;
(2) and sequentially adding a stabilizer, a pH regulator and a cross-linking agent, and uniformly mixing to obtain the profile control agent.
In a third aspect, the invention provides an application of the profile control agent in oil extraction in an oil field.
Through the technical scheme, the profile control agent provided by the invention realizes time-delay controllable crosslinking, and the jelly has certain strength and a sterilization effect, so that one agent is multifunctional.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In a first aspect, the present invention provides a profile control agent comprising: water-soluble thickening agent, modified cross-linking agent, stabilizing agent, pH regulator and water; wherein the modified crosslinking agent is alkylguanidine modified polyethyleneimine.
The inventor of the invention unexpectedly finds that the modified cross-linking agent is obtained by modifying polyethyleneimine with alkylguanidine in research, and is matched with other components of a profile control agent for use, so that time-delay controllable cross-linking can be realized at a higher gelling temperature (50-90 ℃) and a longer gelling time (4-7d), and the jelly has a certain strength, and simultaneously has a sterilization effect, and realizes multiple purposes by one dose.
Preferably, the alkylguanidine-modified polyethyleneimine is prepared by the following method: and (3) carrying out contact reaction on polyethyleneimine and alkylguanidine acetate to obtain alkylguanidine-modified polyethyleneimine.
In the present invention, the polyethyleneimine and the alkylguanidine acetate are commercially available, and preferably, the weight average molecular weight of the polyethyleneimine is 3000-20000.
In the present invention, the alkylguanidine acetate is a long-chain alkylguanidine having a carboxyl group at one end. Preferably, the alkylguanidine acetate is selected from dodecylguanidine acetate and/or octadecylguanidine acetate.
Preferably, the mass ratio of the alkylguanidine acetate to the polyethyleneimine is 0.005-0.2: 1.
In the present invention, the conditions for the contact reaction are not particularly limited, and alkylguanidine modification of polyethyleneimine may be achieved. The inventor finds in research that the alkylguanidine modified polyethyleneimine obtained under the conditions of the temperature of 30-80 ℃ and the time of 1-5h can obtain better effect when used in a profile control agent.
Preferably, the process of the contact reaction comprises: preparing the polyethyleneimine into a polyethyleneimine water solution, and then dripping the alkylguanidine acetate under stirring.
Preferably, the concentration of the aqueous polyethyleneimine solution is 2 to 8 wt%.
Preferably, the method further comprises: and after the contact reaction, carrying out pH adjustment and purification to obtain the alkylguanidine modified polyethyleneimine, wherein the pH is adjusted to 8-12.
In the present invention, the method of adjusting pH is a method commonly used in the art, and preferably, pH adjustment is performed by adding an alkaline substance. The alkaline substance may be sodium hydroxide solution, potassium hydroxide solution, etc.
In the present invention, the purification means may be a purification method conventional in the art, for example, a mixture solution obtained after the reaction is dialyzed in water and then spun to remove water.
According to a particularly preferred embodiment of the invention, the alkylguanidine-modified polyethyleneimine is prepared by the following method:
(1) dissolving polyethyleneimine in water to prepare a polyethyleneimine water solution; wherein the weight average molecular weight of the polyethyleneimine is 3000-20000; the concentration of the polyethyleneimine water solution is 2-8 wt%;
(2) dripping alkylguanidine acetate at the stirring speed of 300-900r/min at the temperature of 30-80 ℃, then continuing to react for 1-5h, and adjusting the pH value to 8-12 after the reaction is finished to obtain a mixture solution; wherein the molar ratio of the dosage of the alkylguanidine acetate to the dosage of the polyethyleneimine is 0.05-0.2: 1.
(3) And dialyzing the mixture solution in water for 1-3d, and then removing water by rotation to obtain the alkylguanidine modified polyethyleneimine.
In the present invention, preferably, the water-soluble thickener is contained in an amount of 0.1 to 3 wt% based on the total weight of the profile control agent; the content of the modified cross-linking agent is 0.1-1 wt%; the content of the stabilizer is 0.05-2 wt%; the content of the pH regulator is 0.01-0.2 wt%; the water content is 93.8-99.74 wt%.
In order to further obtain better effect, in particular to enable the profile control agent to realize time-delay controllable crosslinking at higher gelling temperature and longer gelling time, and the gel strength is better, the bactericidal effect is better, and more preferably, the content of the water-soluble thickening agent is 0.4-2 wt% based on the total weight of the profile control agent; the content of the modified cross-linking agent is 0.2-0.6 wt%; the content of the stabilizer is 0.07-1 wt%; the content of the pH regulator is 0.01-0.1 wt%; the water content is 96.3-99.32 wt%.
In the invention, preferably, the water-soluble thickener is polyacrylamide, the weight average molecular weight of the polyacrylamide is 300-3000 ten thousand, and the hydrolysis degree is 3-7%;
and/or the presence of a gas in the gas,
the water-soluble thickener is a copolymer, and the copolymer is obtained by copolymerization reaction of an acrylamide monomer, an N, N-dimethylacrylamide monomer and a monomer shown in a formula (1); wherein the acrylamide monomer, the N, N-dimethylacrylamide monomer and the monomer represented by formula (1) are used in amounts such that the copolymer obtained contains 60 to 98 wt% of structural unit A provided by the acrylamide monomer, 1 to 39 wt% of structural unit B provided by the N, N-dimethylacrylamide monomer and 1 to 39 wt% of structural unit C provided by the monomer represented by formula (1);
wherein, in the formula (1), R1、R2、R3Each independently is H, C1-C12Alkyl of (C)6-C12Substituted or unsubstituted aryl of (a); r4Is C1-C12Alkyl of (C)6-C12Substituted or unsubstituted alkyl, C6-C12Substituted or unsubstituted aryl of (a).
In the present invention, the polyacrylamide may be commercially available.
The polymer may be prepared according to the method disclosed in CN108017754A, which is hereby incorporated in its entirety into the present invention, CN 108017754A.
In the present invention, the stabilizer may be commercially available. Preferably, the stabilizer is selected from at least one of sodium thiosulfate, sodium sulfite, sodium bisulfite, sodium dithionite, isoascorbic acid, and thiourea.
In the present invention, the pH adjustor may be an alkaline substance commonly used in the art for adjusting pH. Preferably, the pH adjusting agent is selected from at least one of sodium hydroxide, sodium carbonate, sodium bicarbonate, sodium acetate, and ammonia water.
In the present invention, the water is preferably oilfield injection water having a mineralization degree of 5000-.
In a second aspect, the present invention provides a method of preparing a profile control agent according to the first aspect of the present invention, the method comprising:
(1) adding polyacrylamide into water under stirring state until the polyacrylamide is uniformly dissolved;
(2) and sequentially adding a stabilizer, a pH regulator and a cross-linking agent, and uniformly mixing to obtain the profile control agent.
The definitions of the stabilizer, the pH adjustor and the crosslinking agent are the same as those in the first aspect, and the present invention is not described herein in detail.
In a third aspect, the invention provides an application of the profile control agent in oil recovery in an oil field.
Compared with the prior art, the invention has the following advantages:
the profile control agent can realize time-delay controllable crosslinking at a higher gelling temperature (50-90 ℃) and a longer gelling time (4-7d), and the jelly has certain strength and a bactericidal effect, and can be applied to water shutoff and profile control in the oil extraction process of an oil field.
The present invention will be described in detail below by way of examples. In the following examples and comparative examples,
the complex viscosity was measured using a rotational rheometer (available from seimer fisher technologies ltd., RS 6000).
The polyethyleneimine is purchased from Shanghai Aladdin Biotechnology, Inc., and has a weight average molecular weight of 15000.
Dodecyl guanidine acetate and octadecyl guanidine acetate were purchased from carbofuran technologies, inc.
Polyacrylamide was purchased from Shandong Baommo Biochemical industries, Ltd, and had a weight average molecular weight of 2000 ten thousand and a degree of hydrolysis of 5%.
Polymer M was prepared according to CN108017754A, example 1, having a solids content of 87% and a molecular weight of 2000 ten thousand.
Polymer N was prepared according to CN108017754A, example 2, having a solids content of 90% and a molecular weight of 1950 ten thousand.
Preparation example 1
Preparation of dodecyl guanidine modified polyethyleneimine
(1) Dissolving 20g of polyethyleneimine in deionized water to prepare a 5 wt% polyethyleneimine water solution;
(2) 0.344g of dodecylguanidine acetate is dripped into the mixture at the temperature of 50 ℃ and the stirring speed of 600r/min, then the reaction is continued for 2 hours, and after the reaction is finished, the pH value is adjusted to 10 by using 1 wt% of sodium hydroxide solution to obtain a mixture solution.
(3) And dialyzing the mixture solution in deionized water for 2d, and then rotatably removing water to obtain the dodecyl guanidine modified polyethyleneimine.
Preparation example 2
Preparation of octadecylguanidine-modified polyethyleneimine
The procedure of preparation example 1 was carried out, except that 0.344g of dodecylguanidine acetate was replaced with 2g of octadecylguanidine acetate, to give octadecylguanidine-modified polyethyleneimine.
Example 1
Dissolving 11.5g of polymer M in 1000g of oilfield injection water, and stirring at a rotating speed of 500r/min until the polymer M is uniformly dissolved; then sequentially adding 1.05g of sodium thiosulfate, 0.15g of sodium hydroxide and 5.5g of dodecyl guanidine modified polyethyleneimine, uniformly stirring to obtain a profile control agent, wherein the profile control agent starts to form gel after 5 days at 80 ℃, and the composite viscosity reaches 18450mPa & s after the crosslinking reaction is finished.
Example 2
Dissolving 10.5g of polyacrylamide in 1000g of oilfield injection water, and stirring at the rotating speed of 500r/min until the polyacrylamide is uniformly dissolved; then, 1g of thiourea, 0.2g of sodium hydroxide and 5g of dodecyl guanidine modified polyethyleneimine are sequentially added, the mixture is uniformly stirred to obtain the profile control agent, the profile control agent starts to gel after 7 days at the temperature of 55 ℃, and the composite viscosity reaches 17600mPa & s after the crosslinking reaction is finished.
Example 3
Dissolving 8.5g of polymer M in 1000g of oilfield injection water, and stirring at a rotation speed of 500r/min until the polymer M is uniformly dissolved; then, 1g of sodium sulfite, 0.25g of sodium carbonate, 0.25g of sodium bicarbonate and 4g of octadecyl guanidine modified polyethyleneimine are sequentially added, the mixture is uniformly stirred to obtain the profile control agent, the profile control agent starts to gel after 4.5 days at the temperature of 90 ℃, and the composite viscosity reaches 19180mPa & s after the crosslinking reaction is finished.
Example 4
Dissolving 9.5g of polymer N in 1000g of oilfield injection water, and stirring at the rotating speed of 500r/min until the polymer N is uniformly dissolved; then, 0.8g of thiourea, 0.45g of ammonia water and 3.5g of dodecyl guanidine modified polyethyleneimine are sequentially added, the mixture is uniformly stirred to obtain the profile control agent, the profile control agent starts to gel after 5.5 days at the temperature of 75 ℃, and the composite viscosity reaches 21150mPa & s after the crosslinking reaction is finished.
Example 5
Dissolving 10.5g of polyacrylamide in 1000g of oilfield injection water, and stirring at the rotating speed of 600r/min until the polyacrylamide is uniformly dissolved; then, 1.1g of sodium thiosulfate, 0.2g of sodium carbonate, 0.2g of sodium bicarbonate and 4.5g of dodecyl guanidine modified polyethyleneimine are sequentially added, the mixture is uniformly stirred to obtain a profile control agent, the profile control agent starts to gel after 6 days at the temperature of 70 ℃, and the composite viscosity reaches 18140mPa & s after the crosslinking reaction is finished.
Example 6
Dissolving 3.5g of polyacrylamide in 1000g of oilfield injection water, and stirring at the rotating speed of 500r/min until the polyacrylamide is uniformly dissolved; then sequentially adding 1.05g of sodium thiosulfate, 0.15g of sodium hydroxide and 7.5g of dodecyl guanidine modified polyethyleneimine, uniformly stirring to obtain a profile control agent, wherein the profile control agent starts to form gel after 4 days at 80 ℃, and the composite viscosity reaches 17550mPa & s after the crosslinking reaction is finished.
Example 7
Dissolving 25g of polyacrylamide in 1000g of oilfield injection water, and stirring at a rotation speed of 500r/min until the polyacrylamide is uniformly dissolved; then sequentially adding 1.05g of sodium thiosulfate, 0.15g of sodium hydroxide and 1.5g of dodecyl guanidine modified polyethyleneimine, uniformly stirring to obtain a profile control agent, wherein the profile control agent starts to form gel after 4 days at 70 ℃, and the composite viscosity reaches 17480mPa & s after the crosslinking reaction is finished.
Comparative example 1
An experiment was carried out as in example 1, except that the dodecylguanidine-modified polyethyleneimine was replaced with polyethyleneimine, the resulting profile control agent started to gel after 1 day at 80 ℃ and the complex viscosity reached 14990mPa · s after the crosslinking reaction was completed.
Comparative example 2
An experiment was carried out as in example 2, except that the dodecylguanidine-modified polyethyleneimine was replaced with polyethyleneimine, the resulting profile control agent started to gel after 2 days at 55 ℃ and the complex viscosity reached 14330mPa · s after the crosslinking reaction was completed.
Comparative example 3
An experiment was carried out as in example 3, except that the octadecylguanidine-modified polyethyleneimine was replaced with polyethyleneimine, the resulting profile control agent started to gel after 1.5 days at 90 ℃ and the complex viscosity reached 16100 mPas after the crosslinking reaction was completed.
Comparative example 4
An experiment was carried out as in example 4, except that the dodecylguanidine-modified polyethyleneimine was replaced with polyethyleneimine, the resulting profile control agent started to gel after 1.5 days at 75 ℃ and the complex viscosity reached 17440mPa · s after the crosslinking reaction was completed.
Comparative example 5
An experiment was carried out as in example 5, except that the dodecylguanidine-modified polyethyleneimine was replaced with polyethyleneimine, the resulting profile control agent started to gel after 1.5 days at 70 ℃ and the complex viscosity reached 14850 mPas after the crosslinking reaction was completed.
Test example
The number of bacteria in the profile control agents of the examples and the comparative examples was measured by the method of SY/T5329-2012, and the bactericidal performance of the profile control agents of the examples and the comparative examples was evaluated, and the results are shown in Table 1.
TABLE 1
| Item | Test results (one/mL) | Item | Test results (personal/L) |
| Example 1 | 3.3*102 | Comparative example 1 | 9.6*104 |
| Example 2 | 5.5*102 | Comparative example 2 | 9.4*104 |
| Example 3 | 6.1*102 | Comparative example 3 | 9.9*104 |
| Example 4 | 8.6*102 | Comparative example 4 | 9.5*104 |
| Example 5 | 6.2*102 | Comparative example 5 | 9.2*104 |
| Example 6 | 3.2*102 | Example 7 | 9.1*102 |
The comparison of the embodiment and the comparative example shows that the profile control agent provided by the invention can realize time-delay controllable crosslinking at a higher gelling temperature (50-90 ℃) and a longer gelling time (4-7d), and the jelly has higher strength and stronger bactericidal action, thereby realizing multiple purposes of one dose.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (12)
1. A profile control agent, comprising: water-soluble thickening agent, modified cross-linking agent, stabilizing agent, pH regulator and water; wherein the modified crosslinking agent is alkylguanidine modified polyethyleneimine.
2. A profile control agent according to claim 1, wherein the alkylguanidine-modified polyethyleneimine is prepared by the following method: and (3) carrying out contact reaction on polyethyleneimine and alkylguanidine acetate to obtain alkylguanidine-modified polyethyleneimine.
3. A profile control agent according to claim 2, wherein the weight average molecular weight of the polyethyleneimine is 3000-20000;
and/or, the alkylguanidine acetate is selected from dodecylguanidine acetate and/or octadecylguanidine acetate;
and/or the mass ratio of the alkyl guanidine acetate to the polyethyleneimine is 0.005-0.2: 1.
4. A profile control agent according to claim 2, wherein the conditions of the contact reaction comprise: the temperature is 30-80 ℃, and the time is 1-5 h;
and/or the contact reaction process comprises the following steps: preparing the polyethyleneimine into a polyethyleneimine water solution, and then dripping the alkylguanidine acetate under stirring.
5. A profile control agent according to claim 4, wherein the concentration of the aqueous polyethyleneimine solution is from 2 to 8 wt%.
6. The profile control agent of claim 2, wherein the method further comprises: and (3) carrying out pH adjustment and purification on the obtained reaction product to obtain the alkylguanidine modified polyethyleneimine, and adjusting the pH value of the reaction product to 8-12.
7. A profile control agent according to claim 1, wherein the water-soluble thickener is present in an amount of 0.1 to 3 wt%, based on the total weight of the profile control agent; the content of the modified cross-linking agent is 0.1-1 wt%; the content of the stabilizer is 0.05-2 wt%; the content of the pH regulator is 0.01-0.2 wt%; the water content is 93.8-99.74 wt%.
8. A profile control agent according to claim 7, wherein the water-soluble thickener is present in an amount of 0.4 to 2 wt%, based on the total weight of the profile control agent; the content of the modified cross-linking agent is 0.2-0.6 wt%; the content of the stabilizer is 0.07-1 wt%; the content of the pH regulator is 0.01-0.1 wt%; the water content is 96.3-99.32 wt%.
9. A profile control agent according to claim 1, wherein the water-soluble thickener is polyacrylamide having a weight average molecular weight of 300-3000 ten thousand and a degree of hydrolysis of 3-7%;
or the like, or, alternatively,
the water-soluble thickener is a copolymer which contains a structural unit A, a structural unit B and a structural unit C, wherein the structural unit A is provided by an acrylamide monomer, the structural unit B is provided by an N, N-dimethylacrylamide monomer, and the structural unit C is provided by a monomer with a structure shown in a formula (1); wherein, based on the weight of the polymer, the content of the structural unit A is 60-98 wt%, the content of the structural unit B is 1-39 wt%, and the content of the structural unit C is 1-39 wt%;
wherein, in the formula (1), R1、R2、R3Each independently is H, C1-C12Alkyl of (C)6-C12Substituted or unsubstituted aryl of (a); r4Is C1-C12Alkyl of (C)6-C12Substituted alkyl of, C6-C12Substituted or unsubstituted aryl of (a).
10. A profile control agent according to claim 1, wherein the stabilizer is selected from at least one of sodium thiosulfate, sodium sulfite, sodium bisulfite, sodium dithionite, erythorbic acid, and thiourea;
the pH regulator is at least one selected from sodium hydroxide, sodium carbonate, sodium bicarbonate, sodium acetate and ammonia water.
11. A method of making the profile control agent of any one of claims 1-10, comprising:
(1) adding a water-soluble thickening agent into water under stirring until the water-soluble thickening agent is uniformly dissolved;
(2) and sequentially adding a stabilizer, a pH regulator and a cross-linking agent, and uniformly mixing to obtain the profile control agent.
12. Use of the profile control agent according to any one of claims 1 to 10 in oil recovery in an oil field.
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| CN103614123A (en) * | 2013-10-21 | 2014-03-05 | 中国石油大学(华东) | Polyethyleneimine jelly profile-control water-blocking agent |
| CN104152126A (en) * | 2014-07-24 | 2014-11-19 | 中国石油天然气股份有限公司 | Foam profile control system suitable for advanced profile control of oilfield and preparation method of foam profile control system |
| CN106634907A (en) * | 2016-09-19 | 2017-05-10 | 中国石油化工股份有限公司 | Polyethyleneimine water shut-off and profile control agent as well as preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103614123A (en) * | 2013-10-21 | 2014-03-05 | 中国石油大学(华东) | Polyethyleneimine jelly profile-control water-blocking agent |
| CN104152126A (en) * | 2014-07-24 | 2014-11-19 | 中国石油天然气股份有限公司 | Foam profile control system suitable for advanced profile control of oilfield and preparation method of foam profile control system |
| CN106634907A (en) * | 2016-09-19 | 2017-05-10 | 中国石油化工股份有限公司 | Polyethyleneimine water shut-off and profile control agent as well as preparation method thereof |
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